The Story of

Chemistry

Anirban Hazra

Design: Madhuvanti Anantharajan

Pune, India, 2006

1
2
 Preface

The Story of Chemistry is about the development of chemistry from

antiquity, to the modern science it is today. Our aim is to make the
history of chemistry accessible to a wide audience, including school
students and non-specialists. We hope our readers enjoy the informal
and graphic presentation of the book.
In the interest of lucidity, we have taken certain liberties in the
layout of the book. For example, text in quotation marks associated
with a scientist may not be verbatim quotes, but rather, a simplified
presentation of the idea. Readers can follow up this book with more
academically rigorous works like The Historical Background of
Chemistry by Henry M. Leicester.
The design, illustrations, layout and digitization of the book have
been done by Madhuvanti Anantharajan. My discussions, debates,
agreements and disagreements with her have, in my opinion,
contributed greatly to improving the quality of the book. I am grateful
to her for being a fantastic partner in this project.
Our book would not have been possible without the generosity
and help of several people. Arvind Gupta at the Science Centre at the
Inter University Centre for Astronomy and Astrophysics (IUCAA) has
been the major driving force for this project. He participated actively at
every stage, right from conceptualisation to editing. Moreover, he
provided all possible logistical support for the project – introducing
the author and illustrator, arranging funding and interacting with the
publisher – which allowed us to focus on the writing and design of the
book without having to worry about anything else. The book would
not have happened without him.
We are grateful to the Science Centre at IUCAA, where most of
the work was carried out. We thank Vidula Mhaiskar, Ashok Rupner,
Samir Dhurde and Arvind Paranjpye for their support, and for staying
back late on several occasions to allow us to work. An added thank
you to Vidula for her help with the illustrations and the periodic table
at the end of this book.
We thank Awanti Seth Rabenhøj, N. Madhavan, Venu Govindu,
Sonali Shah and Amrita Hazra for editing the book and suggesting
improvements.
My parents, both scientists, have been a constant source of
encouragement and have provided valuable inputs for the book. Also,
from a very early age, they have inculcated in me and interest and
excitement for chemistry.
We thank Jamshedji Tata Trust for financial support for preparing
the manuscript of the book.

Pune, India, 2006 Anirban Hazra

3
4
Ch e m i s t r y
is happening all around us! The sun gives us light and
heat, trees grow, animals eat food to produce
energy and dead matter rots. All these are
chemical processes. Thousands of chemical
reactions are happening in our own bodies
all the time – digestion, seeing with our
eyes, feeling with our fingers, growing,
getting old – each of these involves many
many chemical processes.

Though these processes have been around for millions

of years, it is only quite recently that we have begun
to understand them the way we do today. The science
which seeks such understanding is CHEMISTRY.

Chemistry is the
science of
matter
–the science dealing
with the composition
and properties of
substances, and the
changes they undergo.

5
There is another very significant side of chemistry,
that is, its application by humans. The impact of
this can be seen all around in our life today.
Metals, construction materials, soaps, medicines,
paper, plastic...
’t
w asn
t
f i I’d
ni ,
mea istry read
u m o !
Yo che ave t th??
o r h b a
f
ver e a
ne tak
OR

...not to mention
weapons of
destruction,
come to us
through chemical
processes.

6
 Chemical research today is very diverse.
It includes, among other things, developing
a better understanding of how substances
react, how information of hundreds of
books can be stored on a tiny silicon chip,
what new fuel can supply our energy
needs while safeguarding our environment
and how drugs can be designed for a
specific purpose.

To reach this stage of sophistication,

Chemistry has gone through a long and
exciting journey.

In this book, we wil explore

this fascinating history of
chemistry!
Let us begin by going back some

100,000 years...
7
 Humans were already
using

FIRE
– the timeless chemical
transformation! The
ability to use fire greatly
increased the chances of
human survival. Fire
kept away predators,
provided warmth in the
winter and was used for
cooking food.

It was only a question of

time before it was
discovered that fire, apart
from cooking food,
brought about other
transformations too.

8
 5,000 B.C.
This is a conversation that could have
happened around this time
time...

Ancient person 1: This wet clay

below the fire has become hard
and it does not get washed
away by water.

Ancient person 2: That gives

me an idea. Let us give the
clay a shape and put it in the
fire so that we can store things
in it.

Thus pottery was born. To routinely

bake clay pottery, the kiln was made – a
wood oven producing a steady and high
temperature.

One day, an artist potter decorated a pot with some

small green coloured pebbles before inserting it in
the kiln. On removing the pot from the kiln,
something remarkable had happened.

The pebbles had melted and they were shining!

The decorative stones were actually metallic ore.

They had been converted to metal in the
reducing atmosphere of the kiln.

More of the metal was obtained from the coloured

stones by heating in the kiln and it was found to have
curious properties.

9
 This shiny stuff is great! It does not break
like stone. It flattens out on beating and I
can give it whatever shape I like.

BANG
!

NG!
CLA
Metals came into wide use for
decorative items and tools.
Different combinations of
substances were heated in
kilns in order to eextract
xtract
metals.
The metals used were of ten
often

alloys. bronze
(a mixture of copper
and tin) was used
most eextensively
xtensively
xtensively..

10
 ○ ○
○ ○ ○ ○ ○ ○ ○
○ ○
○ ○ ○ ○ ○ ○
○ ○ ○ ○ ○ ○
○ ○ ○ ○ ○ ○
○ ○ ○ ○
○
○ ○ ○ ○○
○

○
○
○ ○ ○

○
○
○ ○

○ ○ ○
○ ○

2,000 B.C. A mixture of sand,,

○ ○ ○
○

limestone (calcium carbonate) ○○

○ ○
○

○
and soda (sodium carbonate) ○
○
○
○

when heated together were ○

○ ○
○
○

found to combine and form ○

○ ○
○

a clear, glossy substance

○ ○

○ ○ ○
○
○ ○ ○

○ ○ – GLASS!
○

○
○
○

○ ○
Several other everyday ○
○
○ ○

○
○

chemical arts existed

○
○

in ancient times. For

○

○
example making
○ ○

○
○ ○

curd,cheese, bread
○ ○ ○

and wine, and

○
○ ○

dyeing cloth.
○

○ ○
○

○ ○
○

○ ○

○
○ ○

○ ○
○

○
○

○
○

○
○

○
○

○
○

○
○ ○

○
○

○ ○
○

○
○

○
○

○ ○ ○
○

○
○

○
○ ○

○ ○

○
○ ○

○ ○
○
○ ○

○ ○
○

○
○ ○
○

○ ○
○ ○ ○
○ ○ ○ ○ ○ ○ ○
○ ○

11
 Humans developed technology and arts to make food
tastier and life more comfortable. But there is another side
to our nature – enquiry into causes of phenomena.

The earliest explanations of natural processes were in terms

of gods, demons, spirits and the like. In a tribe,
there would be certain people – the priests, witch-doctors
and medicine men and women – whose business it was to
understand these supernatural forces and appease them.

When he asks all these

When stupid questions?
en It’s the rain water The steam Oh, that’s
And wh spirit... boils? spirit...
ins? just him...
it ra

As civilizations
evolved and division
of labour became
more specialized,
this group became
more set apart. It
did not have to do
much manual work
and had the leisure
to speculate on the
nature of the world.
This group of
people, the early
philosophers came
up with the first
scientific theories.

12
The development of the first
eks
Gre ite,
theories of chemistry began around ose r
Th e to w y?
the 6th century B.C. in at least
e
lov ’t th
n
do
three civilizations, namely Greek,
Indian and Chinese. Of these, the
work of the Greeks is most
documented and the dates
associated with the events are
known quite accurately. That is
why we will look more at the
theories of the Greeks.

Greek philosophy
began in the city of
Miletus in the region
of Ionia, today the
west coast of Turkey.

13
“Can everything
be regarded as a
single reality,
appearing in “Yes, there is a
different forms?” single reality in
nature and it is
water. It can be
converted to air
(evaporation) and
congealed to a
solid. It can
therefore serve
as the origin of
all things.”

Thales of Miletus
(c. 640 — 546 B.C.)

The states of matter — gas, liquid, solid — and

their interconversions, were the basis for explaining
all changes in nature.

cloud
.
ur
po
va

snow
er
at
w

rain hail

ice

water

Others philosophers in Ionia chose different first

sources like air, fire or a formless infinite substance,
apeiron
14
 The last well known philosopher in Ionia was

Anaxagoras . of Klazomenae. He assumed

that the world is made up of an infinite number of minute
particles which he called “seeds”.

“Seeds contain
extremely small
portions of everything
that exists in the visible
world. The amounts of
these are variable in an
individual seed. Seeds
which contain more
An
a
wood, for example,
(c. xagor tend to group together
499 a
– 42 s
8B
.C .)
to form wood.”

An individual seed which we find in a piece of wood would

look like this. It has portions of all kinds of stuff, but the
largest portion in it is wood.

iron hair water

dry everything
else

wood

blue
flesh wheat

15
 5
90 – 43
e
ily (c. 4 minut r
c f u
m in Si posed o only fo
u
ent re com are of itional
gri g a h d
les of A objects ts whic Two ad trife.
c o . S
m pedo ll visible es or ro d Earth ve and ts
E l n o n
.C .): “A g partic Water a ts are L e eleme
B ngin e, Air, ll objec Love th uence
ch a
un s – Fir ts of a nce of he infl
type ponen e influe under t arate.”
com der th e and ey sep
Un ombin rife th
c t
of S

Before Empedocles, air was often considered a

transition between water and fire, and not really a
material substance. Empodocles recognized that air is
material and showed this by experiment. He used a
clepsydra, a vessel with two holes - one at the bottom
and one on top. When he placed the bottom hole of
the vessel under water, Empedocles observed that the
vessel filled up with water. If, however, he put his
finger over the top hole, then the water did not enter
the hole at the bottom. Once he removed his finger
water entered and air rushed out. The experiment
demonstrated that the air in the container prevented
the water from entering.

16
 trying , but I
Aaargh... I’m
break these atoms up
Here, see if you can

can’t!!
Democritus
of Abdera (c.
460 – 370 B.C.)
“All matter is composed of
collections of infinitesimal and
indivisible particles, that is
atoms (atomos in Greek
means indivisible). The atoms
of the four elements, earth,
air, water and fire have physical
size and shape which explain
many of their properties. The
atoms of fire are round balls
which do not mix with the
other elements. The atoms of
air, water and fire have
geometrical shapes and can
become entangled with each
other to produce visible
substances.”

The idea of atoms, which

has similarities with modern
ideas, is thus ancient.
However during that time,
it was pure speculation just
like any other Greek theory
and did not make any
special impact.

17
ΑΒΓ∆ΕΖΗΘΙΚΛΜΝΞΟ
ΩΑΒΓ∆ΕΖΗΘΙΚΛΜΝΞ
The most influential Greek philosopher was
Aristotle (384 – 323 B.C.), who is also well
known as the tutor of Alexander the world conqueror.

ΖΗΘΙΚΛΜΚΛΜΝΚΛΜ
Aristotle built up a great body of self-consistent theories
(i.e. theories that do not contradict each other)
attempting to explain all nature in a more detailed

ΑΒΓ∆ΕΖΗΘΙΚΛΜΝΞΟ
fashion than any of his predecessors.

“The basis of everything is prote hyle the fixed and

unchanging “first matter” on which are impressed the
ΕΒΓ∆ΕΖΗΙΘΙΚΛΑΒΓ∆
specific qualities that give a substance its
characteristic form. There are four qualities – heat, cold,
dryness and moisture. These can be combined to form

ΑΒΓ∆ΕΖΗΙΙΘΙΚΖΗΘΙΚ
six couples. However, contraries – hot and cold or moist
and dry – cannot couple. Therefore, only four couplings
are possible. These give four elements, which make up

ΓΒΓ∆ΕΖΗΘΙΚΛΗΘΙΚΙ
all earthly matter.”

ΩΑΒΓ∆ΕΖΗΘΙΚΛΜΝΞ
ΑΒΓ∆ΕΖΗΘΙΚΛΜΝΞΟ
ΘΒΓ∆ΕΖΗΘΙΚΛΓ∆ΙΙΕΖHot + Dry = Fire
Hot + Moist = Air
ΛΒΓ∆ΕΖΗΘΙΚΛΜΝΞ∆ Cold + Moist = Water
Cold + Dry = Earth

ΞΒΓ∆ΕΖΗΘΙΚΛΜΝΞΩ 18
18
“Besides these four
elements which
make up all earthly
matter, there is a fifth
element “ether”
which is the more
ideal element, the
perfect form, and of
it the heavenly
bodies are
composed.”

The se qualities could be

These
varied to any degree, and so
it was possible to transform
any element into any other.
For example, to convert
water into air, it is only
necessary that the cold be
overcome by heat
heat,, since the
moist is common to both.
19
 ○ ○ ○ ○ ○ ○ ○ ○
○ ○ ○
○ ○ ○

In India and
China too,
theories of matter were
○ ○

developed, starting around

○
○ ○
○ ○ ○ ○

○
the fifth century B.C.

○
○
○ ○ ○ ○

Kapila, one of the oldest Indian

philosophers said, “There are five
○ ○ ○ ○ ○

bhutas or classes of substances –

○
Akasha (space or ether), Vayu

○ ○
○ ○ ○ ○
○

(air), Tejas (fire), Ap (water) and

○
○

○
○

○
○

○
○
○

Kshiti (earth). These substances are

○

○ ○
○
○

○
made up of Anu or atoms and these
○

○ ○ ○

○
are further made up of intra-atomic
○ ○
○ ○

particles. The difference in grouping

○
○ ○ ○

of intra-atomic particles, give

○

rise to the different

○
○

“Classes of
substances??! properties of substances.”
I never knew
that! I thought
we bhutas were
just spirits who ○
○
like to scare you ○
○
folks and have ○
○ ○
a bit of ○
fun!”

20
Kanada, another Indian philosopher suggested:
“Akasha or ether has no atomic structure; it is inert
and ubiquitous. There are four kinds of atoms air,
fire, water and earth and these combine with each
other to form molecules. The variety of substances
is the consequence of the difference in the
molecular composition. Heat corpuscles cause
transformation of substances.”

The Chinese had a theory of the

constitution of matter based on 5 elements:
wood

water fir
iree

metal earth
The combination of these gave rise to all material
substances. Properties of these substances were
summed up in the two great contraries: YIN the
female principle associated with the moon, night and
heavy, and YANG the male principle associated
with the sun, day and light.
21
 In Aristotle’s later years, his famous pupil
Alexander (356 – 323 B.C.), set out to
conquer the world. His conquests brought the world
closer and allowed different philosophies, religions and
ideas to mix. A common culture – the so called Hellenistic
culture – spread in the whole of the area around West
Asia. In this melting pot arose the new idea of alchemy.

Alexander’s conquered
territory

Seas

MACEDONIA

BACTRIA

PARTHIA
MESOPOTAMIA

Alexandria
Babylon
INDIA

Alexander’s conquest route

1st century A.D.

Alexandria, a settlement founded by Alexander at the mouth
of the Nile became a chief centre of intellectual activity.

Hero (c. 52 – 150 A.D.)

developed mechanical devices like a
steam engine and a mechanism that
would deliver holy water when a coin
was deposited (a slot machine). He
studied the nature of gases and in
many respects anticipated the Hero’s steam engine may
kinetic theory of gases. have looked like this...

22
In Alexandria, a number of eastern mystical religions
established themselves and these influenced the
natural philosophers. Also present were the artisans
who produced the luxuries for the wealthy classes and
the temples. The artisans came in contact with the
theories of the philosophers and from this union of
theory and experiment came a totally new growth...

Alchemy was thus a result of various ingredients –

Greek and east ern philosophies, elements of
eastern
mysticism
mysticism,, and Egyptian ttechnology
echnology

Alchemy was grounded in

Aristotelian ideas. One of
these was that all things
tend to reach perfection
and this implied that among
the metals, the less perfect
were always striving to reach
the perfection of gold.
23
 Nature carried out this perfection
process of creating gold deep in the earth
and over a long period of time. The artisan
in his workshop could repeat much of this
process in a relatively short time by improving
his methods and make pure gold with his own
abilities. This was the basic idea of alchemy.

“We know how to convert rocks to

metal – since we can do that, I am sure
we can convert a less perfect metal to
gold as well. I am certain that a metal
which closely resembles gold, is
actually a form of gold. It may be
somewhat less perfect, but with only a
little effort it can be transformed into
the perfect metal.”

Alchemy was thus an extension of the

metallurgical practices of the day.
24
 Colour of the metal was
considered a fundamental property.

“We, of course, want yellow metal. We

will extract the ‘spirits’ of eggs, which
on distillation will yield a substance
(which people will later call sulphur)
that will colour metal yellow.”

○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Later... Well, that didn’t

work, but I think I
just invented the
omelette!

25
 Alchemy developed in
parallel in China with its
basis in Taoism, a school of
philosophy founded by Lao
Tzu in the 6th century
B.C. The Chinese alchemist
wished to make gold not
merely for the sake of gold
itself. He believed that by
eating gold, or some similar
preparation, he could attain
eternal life and have limitless
powers. There is thus a
considerable amount of
alchemical literature on
methods of consuming gold
to achieve immortality.

That’s a nice Oh, it’s actually

pendant! my lunch

26
The name chemistry initially
makes its appearance in the earliest alchemical
recipes around the first century A.D. It may have
come from the Egyptian word “khem”, which is
the ancient name of Egypt and which was a
prominent centre for chemistry at the time.

A second theory is that chemistry comes from the

Greek “cheo”, which means, “I cast”, or “I pour”,
and refers to the metallurgical operations of early
chemists. Yet another suggestion is that chemistry
is derived from the Chinese “chin-i”, pronounced
“kim ya”, which means “gold making juice”.

27
About 300 A.D
Alchemy spread from
Alexandria to Syria,
Mesopotamia (Iraq)
and Persia (Iran).

622 A.D. Islam spread rapidly through all Arabia.

Around this time scholarship flourished. The Arabs inherited
a rich intellectual legacy from the Greek and the Chinese.
The addition of the Arabic definite article “al” or “the” gave
the word alchemy – meaning “the Egyptian science”.

Jabir ibn Hayyan (Geber) (c. 721 – 815)

was the most celebrated of the Arabian alchemists.
According to the Jabir system heat, cold, dryness and
moisture were actual natures which had an independent and
concrete existence. So for example pure Cold could be
obtained separately. The task of the alchemist was to
determine the proportion in which these natures entered into
substances, to prepare the pure natures, and to combine
them in the proper amounts to give the desired products.

In an attempt to prepare pure natures,

many chemical operations and
practical laboratory
apparatus were developed.
The Jabir works describe
the destructive distillation
of a very large number of
substances including
animal products. It
was also believed that
silver can be
converted to gold by
using an “elixir”.
28
But the Bi Bigg
Questi
Questi on sti
stion stillll
rem aine
ainedd....
emaine

The big question is,

“How do we make the
elixir? ”.

29
Al-Razi (Rhazes) (c 860 – 925), another
great name in Arabian alchemy, was a physician who in his
work brought a practical, scientific approach to chemistry.
His writings were free from mysticism and allegory. They
contain discussions of apparatus, classification of substances
and technical recipes. A major contribution is the recipes
for sharp waters, that is alkalis and acids which can be used
as solvents for metals and other substances.

Hello, I am Abu Bakr Muhammed

ibn Zakaria al-Razi. But you can
call me al Razi. Here is my recipe
for preparing sharp water:
Take equal parts of
calcined al-Qili (sodium
carbonate) and unslaked
lime and pour over them
4 times their amount of
water and leave it for 3
days. Filter the mixture,
and again add al-Qili and
lime to the extent of one-
fourth of the
filtered solution.
Do this 7 times.
Pour it into half
(the volume) of
dissolved sal
ammoniac. Then
keep it; for verily
it is the strongest
sharp water. It will
dissolve Talq
(mica) immediately.

30
11th, 12thand 13th centuries A.D
A number of alchemical books and commentaries on older
writings came out, but they added almost nothing new. Mystical
ideas prevailed and science in this region lost its drive. Fortunately,
at this time Western Europe, which would have been quite
unready to receive Greek scientific ideas at an earlier period, was
able to accept the theories of the Arabs and thus the tradition of
science was not lost.

The theories of the Arabs were now passed on to the West. A large
number of Arabic alchemical manuscripts were translated to Latin.
Western Europe now took over as the chief centre for alchemy.

Better glass was used,

developed by artisans in
Italy and distillation
apparatus was improved.

31
It became possible to prepare strong solutions of alcohol, which
was known as aqua vitae, water of life. Nitric acid and aqua
regia, an acid (mixture of nitric and hydrochloric acid) which
dissolves gold became common reagents and were produced on
a large scale. This greatly increased the power of the chemist to
dissolve substances and carry out reactions in solution.

hydrochloric nitric acid aqua regia

acid

An alchemist’s lab
32
 Gu
np
wa
wo s m
uld anu

ow
f
re it hav act
sp is e l ur
o f a e
sys nsib elt t rge d an
t l
der
h
inv em e fo at mpl d u i
en in r t to ica sed
tio W he a l tio in
e a
Ch n of ste ove rge ns f war
ina gu rn E rth ex or fa
in npo ur row ten soci re. T
th w op t e
e 1 de e ( of t it w ty a his
r
0 th t T h h as nd
ce ook e a e fe
nt c u
ur plac tua dal
y). ei l
n

14thand 15th centuries A.D.

There was a lot of activity, but most of it centred
around experiments following old alchemical recipes.
Alchemists produced more and more manuscripts, which
merely repeated earlier ideas in different words.

They worked like madmen, often in secret. They hoped to

fashion the “philosopher’s stone” – a mythical substance
which could turn baser metals to gold.

33
 But every time the day for
testing came…

Hold your We are

breath! about
to
witness
history!

34
The story was always the same...
Failure!
35
There was an increasing tendency toward
allegory and mysticism, and charlatans
were frequent. Alchemy had reached a
dead end now.

“It’s time to admit

it now – TO MAKE
GOLD, ONE MUST
START WITH
GOLD!”

Though the goal

of alchemy was not reached,
a number of useful tools and processes
had been developed on the way. Apparatus
like stills, furnaces, water baths, retorts,
distilling flasks, beakers and filters were
invented. Modified versions of these are still
used today. Metallurgy developed greatly. The
gold cooks laid down elaborate recipes –
extraction of gold by amalgamation with
mercury and the preparation of caustic alkali
from the ashes of plants. They also
developed many new
manufacturing processes.

36
16th century A.D
The work of practical chemists took chemistry forward.
Quantitative methods in metallurgy like assaying
(analysing an ore or alloy to determine the quantity of
particular metals in it) and testing ore quality developed.
Books were published which gave detailed descriptions
of the practice of mining, the treatment of ores, and the
preparation of reagents.This was a period when the
technological branch of chemical science progressed
while the theoretical side remained relatively inactive.

In 1500, Hieronymus Brunschwig (c.1450 - 1513)

published an important book, the Liber de arte
distillandi. The book contained an exposition of the
methods and apparatus of distillation of plant or
animal products, mainly by steam. The
book reveals great originality;
primarily because of the
description, complemented by
abundant illustrations, of
chemical and distillation
apparatus. Brunschwig
frequently used a water bath
in his distillations, and
condensed the plant
essences in a conical
alembic cooled by air,
which was called a
Rosenhut
Rosenhut.

37
One of the controversial figures of the sixteenth century
was a man called Philippus Theophrastus Bombastus
von Hohenheim (1493 – 1541), who called himself
Paracelsus. He laid stress on iatrochemistry, that
is, the use of chemistry for healing human illnesses.

He was controversial because of his volatile temper

and sharp criticism of earlier alchemists as well as
doctors and apothecaries of the day. To prepare
medicines, Paracelus, subjected
a large number of metals to a
standardised set of
reactions. He thus
obtained a series of
salts of various
metals in solution.
For the first time, he
generalised chemical
reactions instead of
considering every
process as a
different
transformation.

38
 17th century A.D

Goodbye
Aristotle!
Thanks for
everything!

Chemistry began to assume the

position of an independent science
and patterns of chemical thinking
and philosophy emerged. Also,
some ideas, particularly Aristotelian
which had stood for more than two
decades underwent upheaval.
39
Van Helmont (1577 – 1644) a wealthy
physician living near Brussels, spent most of his life in
retirement, carrying out chemical experiments. He felt that
water could be converted into other substances and to prove
this he did the following experiment.

He planted a tree in a weighed amount of earth, watered it for

five years, and then showed that, while the tree had gained 164
pounds, the weight of the earth remained the same.

To him, this proved that all parts of the tree had formed from
water and thus that water was the basis of all chemical
substances. Though the fallacy of this would be shown later,
the idea of quantitative experiments was established and so
was the implicit assumption that matter is not created or
destroyed in the changes that it undergoes.

5 years
later

This also proves that

you need bigger
beakers to grow trees

40
Johann Rudolf Glauber (1607 – 1670) was
self-taught in chemistry, and he wandered over much
of Europe learning methods used in various
countries. He eventually settled down in Amsterdam,
where he constructed an excellent laboratory.

“Salts are made of two parts, one coming from

an acid, the other from a metal or its earth
(oxide). Salts can react with each other or acids
to produce new salts. Acids have different
strengths - a stronger acid reacts with a salt of
a weaker acid. For example, nitric acid reacts
with sal tartari (potassium carbonate) to give
saltpetre (potassium nitrate) with the
evolution of a gas (carbon dioxide).”

Glauber’s name comes up most often in the

context of the salt sodium sulphate which he
prepared and attributed marvellous powers
to. It had been since known as Glauber’s salt.

41
In the 17th century, there was a major change in
the theoretical basis of chemistry. There was a
shift from the Aristotelian theory that led to the
belief that every chemical change is a
transmutation, that is, the reaction products are
completely new and nothing of the old substance
remains. Evidence accumulated from experiments, to
indicate that the same substance could persist
through a series of chemical changes. It was
natural to assume that there existed some
unchangeable property of the element that carried
through all the steps. It was time for a revival
of the atomic theory of Democritus.

Joachim Junge (1587 – 1637), explained many

reactions in atomic terms: The replacement of iron
by copper, on the surface of an iron piece placed in
a copper sulphate solution, is not a transmutation,
only an exchange of atoms.

iron key

copper sulphate
solution

42
Irish-born Robert Boyle (1627 – 1691) was an
amateur investigator working in England. Based on his
experimental work he enunciated the inverse relationship of
pressure and volume of gases.
t! I
t m e ou re
! Le pressu
argh e
“Aa take th re!”
n’t m o
ca ny
h e re a
in

Boyle said, “Corpuscles –

small, solid, physically
indivisible particles are the
building blocks of nature.
Corpuscles are associated
into larger groups through
a number of chemical reactions. These groups act
as units and the size, shape and motion of these
units give substances their properties.”
Democritus’s idea of atoms was back. Boyle however did not use
the word, rather choosing to use corpuscles. Boyle attempted to
present a mechanical picture of chemical reactions, doing away
with the idea of forms and qualities of Aristotle.

43
Boyle’s famous book The Sceptical Chymist published in 1661
presented convincing arguments to destroy most of the older
ideas. The book is written in a rather prolix style and enlivened
with touches of humour, as when the alchemists are compared
with “the Navigators of Solomon’s Tarshish Fleet, who brought
home . . . not only Gold, and Silver, and Ivory,
but Apes and Peacocks too”, since their
theories “either like Peacock’s feathers
make a great show, but are neither solid
nor useful; or else, like Apes, if they
have some appearance of being
rational, are blemished with some
absurdity or other which makes
them appear ridiculous.” The
book was extremely influential in
establishing a newer outlook
among chemists of the 17th
century.

al
e p tic 680
Sc n, 1
T he ditio
of de
p age econ
le ,s
Tit ymist
C h

In the 1640s, scientists began organizing groups to meet and

discuss the problems they faced in
their laboratories. At first these
were informal meetings and they led
to formal organizations. One such
group was the Invisible College,
of which Boyle was a member.
This group met at Oxford and
in London and from this arose
the Royal Society (a scientific
academy) in London in 1662.

44
 Late 17th century
The attention of scientists was centred around
understanding the nature of combustion and the
forces that hold chemical compounds together.

While observing something burn, the flame seemed

to be escaping from the object, so something
seemed to be lost in the process. The relatively light
ash left when an organic substance was consumed
corroborated this. The practical metallurgists knew
quite well that when metals were heated they were
converted to a heavier powder, but they did not
connect this to burning of organic substances.

Experiments showed that air was required for

combustion. For example, Boyle tried to burn sulphur
in a vacuum and failed. This proved that burning
required air.

45
45
 J
ohann Joachim
Becher (1635 –
1682) in
Germany felt that
substances which could
burn contained a fatty
component called “terra
pingus” and this left the
substance during
combustion.

This idea was taken up by his pupil Georg Ernst

Stahl (1660 – 1734), who further developed
this idea and came up with a theory to explain
the process of combustion. To the fatty earth,
Stahl gave the name phlogiston from the
Greek word for “burned” or “inflammable”.

“When combustion
occurs phlogiston is lost
from the substance and air
is essential as the medium to
carry away the phlogiston. Metal
when heated loses phlogiston
l
Stah

and is converted to calx (oxide).

The metal is therefore a more
complex substance than
the calx.”

46
 “Plants absorb phlogiston
from air and are rich in
phlogiston. Plant substances
can react with metal calces
to restore the phlogiston and
convert them to metals
again. Charcoal is extremely
rich in phlogiston and the
most useful substance for
this purpose.”

Phlogiston theory supplied an

excellent explanation for the then
known facts about combustion.
Oxidation-reduction was explained,
though the explanation was essentially
the reverse of what we think. So, for
example, during oxidation, we consider
a substance oxygen to be taken up.
However, Stahl considered a substance
phlogiston to be given off.

But, there was an apparent inconsistency.

When organic substances burned, the
product weighed less than the original
substance. The problem arose with the
calcination of metals. This was recognised
as the same process, but the products
weighed more than the original substance.
To Stahl this was not important. He
thought of phlogiston as a “principle” that
could not be known directly, rather than a
definite physical substance. This
abstractness of thinking when faced with
inconvenient facts would, in time, lead to
the downfall of the phlogiston theory.
But as of the mid-1700s, the phlogiston theory was almost
completely accepted.
47
Side by side, theories of chemical affinity –
the “force” causing reactions – developed.
Affinity was considered in terms of
Newton’s ideas (which were gaining wide
acceptance at the time for explaining
physical phenomena) that every particle of
matter was endowed with a certain attractive
force that uniquely caused all its chemical and physical reactions.
To make the concept generally useful, chemists felt the need to
draw up tables of affinity that would express the reactivity of
individual compounds toward each other. They also hoped that
such tables could be used to predict the reactivity of other
compounds in similar reactions.

The table of Etienne-Francois Geoffrey

(1672 – 1731) arranged substances in columns, with their
respective alchemical symbols at the head of each column. The
rest of the column listed substances that were found by
experiment to react with the substance at the head. The
arrangement was such that, the lower you go in each column, the
lesser the affinity the substance had, for the one at the head. In
other words, each column was arranged in a descending order of
affinity for the substance at the head.

The compilation of these tables became more difficult as the

number of known chemical compounds increased.

48
 Till now gases were thought to not
take part in chemical reactions. The greatest
advance in laboratory discoveries of the 18th
century lay in the isolation and identification
of gases as chemical individuals.

An English clergyman Stephen Hales

(1677 – 1761) investigated the amounts of “air”
that were evolved from different substances by
heating. In the course of this work he
perfected the
pneumatic trough
gas entering
trough

to collect, over
water, the gases gas

that were formed. collected

after

This apparatus was

displacing
water

of great value to
later workers in
the field of gas
chemistry.

Hales’s pneumatic trough

49
In Scotland, Joseph Black (1728 – 1799) conducted
studies on gases which were part of his thesis for the
Doctor of Medicine at the University of Edinburgh.

“A gas is lost on heating “We have seen that a gas can

limestone (CaCO3) and react chemically. The gas
it is converted to (CO2) can be fixed in solid
quicklime form so
(CaO). lets call it
Treatment of ‘fixed air’”.
the quicklime
with ‘alkali’
(sodium
carbonate)
gives the
original
limestone.”

This work completely altered the thought of chemists.

For the first time it was shown that a gas could
combine chemically with a solid (be “fixed” by it) to
produce a new compound with different properties,
instead of being held by some indefinite physical force.
50
 A practical
Dissenting English clergyman, result of
Joseph Priestley Priestly’s
studies with
(1733 – 1804), was an amateur
carbon dioxide
chemist. He was completely
was that in
untrained in chemistry and did not
1772, he
begin chemical investigations till he
invented soda
was thirty eight years old. He
water!
happened to live next to a brewery
from which he could obtain a large
supply of carbon dioxide. This
allowed him to study the gas and
find that it extinguishes burning
chips of wood.

Priestley used mercury instead of

water in a pneumatic trough and he
was thus able to isolate gases which
until then could not be isolated
(because they dissolve in water).
Priestley was the first to isolate and
characterise the gases nitric oxide,
carbon monoxide, sulphur dioxide,
hydrogen chloride and ammonia.

red precipitate

1774. By heating “red

precipitate” (mercuric oxide
though it was not known
then), with a lens, he
obtained a colourless lens
odourless gas. A candle
burned more brightly in the
water
presence of the gas. Animals
lived longer in a sealed jar

51
containing the gas “This gas is
than in a jar of ‘dephlogisticated air’
atmospheric air. because it has a great
Priestley had capacity to absorb
phlogiston released
discovered oxygen.
during combustion.”

This gas was independently discovered by another

scientist CARL WILHELM SCHEELE (1742 – 1786).

This image is reproduced from Priestley’s book, Experiments and

Observations on Different Kinds of Air. It shows Preiestley’s
apparatus for experiments with gases; the large vessel is a pneumatic
trough, and there are mive and plants in the inverted jars.

Priestley also
discovered that green
plants give off
dephlogisticated air in light,
which was the basis for all
later studies in
photosynthesis.

52
There was a large amount of experimental data available now
which could not be explained by phlogiston theory.

Antoine Laurent Lavoisier (1743 – 1794), a

wealthy Frenchman, came up with a theoretical framework for
understanding combustion and other chemical reactions which
placed chemistry on an essentially modern basis.

This step is often called the

Chemical Revolution
“Calcination of metals
is analogous to the
burning of phosphorus
and sulphur, and
involves a combination
with air.”

1770s Antoine Laurent Lavoisier

He performed an experiment where tin was calcined
in a sealed vessel where it was partly converted to
calx (oxide), but there was no gain of weight until
the vessel was opened. When this was done, air
could be heard rushing in. There was no doubt that
the increase in weight when a calx was formed came
from a combination of the metal with air. Thus it
was realized that the metal is a simpler substance
than the calx unlike what was thought in the
framework of the phlogiston theory.
53
 “I found that air is a mixture of two substances – to the purer
part, which is used in respiration and in calcinations of
metals, we give the name oxygen and the residue we
will call mofette. I later decided to call the residue
azote, from the Greek term meaning ‘without life’. In
1790, Jean Antoine Chaptal gave it its modern
name, nitrogen.”

“Phlogiston theory has several weaknesses, which can

be avoided if it is recognized that, in every
combustion, combination with oxygen occurs, with
evolution of heat and light.”

The final step required for completing

Lavoisier’s theory was understanding the

composition of WATER.
In 1781, Joseph Priestley and Henry Cavendish
observed droplets condensing in the vessels
in which “inflammable air” (hydrogen) burned.
These droplets were shown to be water. A
couple of years later, Lavoisier came up with
an explanation for this...

“Water is a compound of inflammable air (the

name for hydrogen given by its discoverer
Cavendish) and oxygen.”

54
 178
che 9, Pa
é l é m istry r i s : A
m
e by
whi entair Lav te
oisi xtboo
ch r e d e ko
phlo ejec e ch r, T f
g i
e s s e ston d t h rt e i m ie w té r a i
com n t i a l l y theory o u g h e a s p u b
m l
of s bustio o d e r and p x p e r i m i s h e d ,
imp n. T n ex r ovi ent
nat
u r e le subs he bo p l a n a t ded th s , t h e
vari , t o io e
ous w h i c h a n c e s k also n f o r n e w ,
true b m be co
t a b odies i a y b e l o n g i n ntaine
le o c
f c h n natu o n s i d e g t o a l d a “ta
em re”. red l kin ble
ical T
e l e m his is t h e e l e g d o m
e n t consi m e n s o f
s. der t
ed t s o f
he f
irst

The book also represents the fermentation

process in the following way:

must of grapes = carbonic acid + alcohol

This is the forerunner of a modern chemical equation.

Lavoisier at the age of fifty was guillotined in 1794 during the

frenzy of the French Revolution.

55
In 1799 French chemist Joseph
Louis Proust (1754 –
1826) who taught at Madrid
demonstrated practically the law
of constant proportions: He
showed that, in copper
carbonate, the proportions by
weight of the elements that
constitute it, are fixed, no
matter how it is prepared and
whether it occurs naturally or is
prepared by synthesis.
In Manchester,
John Dalton (1766 – 1844)
developed an atomic theory which would
explain the observations of Proust and
provide a basis for considering compounds
the way we do today.

“Atoms are dense spheres and

are of different sizes for
different substances. A
compound of two substances
(a binary compound) contains
one atom of each of the two
constituents. Water is a
compound of one atom of
hydrogen and one of oxygen,
ammonia one of hydrogen and on
D alt
one of nitrogen and so on.” hn
Jo

56
Pages from Dalton’s book A New System of Chemical Philosophy

Based on this assumption, after chemical analysis of

compounds, Dalton obtained relative weights of atoms. The
analysis of water available to him showed that it contained 85 2/
3 parts of oxygen and 14 1/3 parts hydrogen. If the relative
weight of hydrogen was taken as unity, the relative weight of
oxygen became 6. In a similar way, Dalton came up with relative
weights of other atoms and drew up the first table of atomic
weights.

Dalton devised a set of symbols to express his theory. The

graphic nature of the theory helped in its acceptance.

57
 Swedish chemist, Jöns Jacob Berzelius
(1779 – 1848) recognized that in a compound
one atom of an element might combine with
varying numbers of atoms of other elements, and
that two atoms could combine with multiple
numbers of other atoms.

1809. French chemist, Joseph Louis

Gay-Lussac (1778 – 1850) proposed, “ The ratios
of the volumes of reacting gases are small whole
numbers – hydrogen and oxygen unite in the
proportions 2:1 to form water, 1 volume of nitrogen
and 3 of hydrogen combine to from ammonia.”

hydrogen oxygen water

(gaseous state)
58
 1811. Italian, Amadeo
Avogadro (1776 – 1856)
said, “Equal volumes of
different gases contain
same number of particles.
Thus the ratio of the
densities of two gases (at
the same temperature and
pressure) represents the
ratio between the masses
of their particles.”

Avagadro assumed that atoms of a simple gas

could combine with each other to form a
molecule (like O2, H2) and in reaction with
another gas, these molecules could split apart
to form new molecules. “The molecule of
water will be comprised of half a molecule of
oxygen with one molecule, or two half
molecules of hydrogen”.

It was hard for scientists to conceive of two

like atoms uniting and there were not enough
facts confirming Avagadro’s hypothesis, so
there was half a century of confusion before it
was finally accepted.

59
 1814. Berzelius drew up a table of atomic
weights that is very close to that used today. The
fact that numerical calculations could be applied
to chemical equations and that each element was
recognized as having certain fundamental
characteristics greatly systematized chemistry.

The systematization became more pronounced

when Berzelius introduced modern chemical
symbols,, which was a convenient shorthand
to represent compounds. The initial letter of the
Latin name of the element was used and when
names began with the same letter, the next
distinctive letter of the name was to be added.
A symbol represented one atom or atomic
weight of the element.

Element Latin name Symbol

Sulphur Sulphur S
Silicon Silicium Si
Antimony Stibium St *
Tin Stannum Sn

* Some modifications have been made to Berzelius’s symbols.

Antimony is a case, whose present symbol is Sb.

60
A new direction for scientific exploration opened up
around this time due to the discovery of electricity
from chemical reaction.

The way to generate electricity known at the time was

by rubbing together certain materials. The discovery
of chemical electricity happened by chance.

In 1786, Luigi
Galvani (1737 –
1798), professor of
anatomy at the University
of Bologna hung a
dissected frog muscle on a
copper hook placed on an
iron support. The muscle
twitched. Galvani sought
an explanation for this
interesting phenomenon.
Being a biologist, he
centred his attention on Luigi Galvani
the muscle. He thought
electricity arose in the
muscle causing it to twitch.

I
remember
getting an
electric shock
from an eel.
Animals do
produce
electricity!

61
 Fellow countryman,
Alessandro Volta
(1745 – 1827) thought,

“Maybe it is
the contact of
different metals in a
moist environment
that causes the
electricity and the
muscle is only an
indicator.”

Volta performed an experiment where he arranged

silver and zinc plates separated by cloth soaked in
brine. He found that this produced electricity and
the effect increased with more such junctions.

The Voltaic pile was

the first true battery, and
from it came a continuous
current whose effects
could be increased by
merely increasing the size
and number of alternating
plates. Almost at once
chemists began to use this
new apparatus to produce
chemical reactions.
A Voltaic pile

62
Humphry Davy (1778 – 1819), a professor of
chemisty at the Royal Institution in London, constructed a
battery of over 250 metallic plates. In 1807, using electricity
from this battery, he was able to extract highly reactive metals
like potassium and sodium by electrolysis of fused salts.

Davy made several other

important contributions to science
including designing a lamp which
was safe for miners to use in
methane rich atmospheres
(methane is highly inflammable).
Davy’s safety lamp

Davy had chosen Michael Faraday (1791-1867) as his assistant

while at the Royal Institution. This is a famous conversation
between Davy and a journalist:

Mr. Davy,
what is your
greatest My greatest
discovery? discovery is
Michael
Faraday!

63
Michael Faraday’s father was
a blacksmith and could not
afford to give him a formal
education. Faraday worked
with a bookbinder. This job
gave him two things – a
large variety of books to
read and a training in using
tools with precision and
dexterity. His deep interest
in science got him in
contact with Davy where he
flourished as a scientist.

1833. In electrolysis
the amount of
substance decomposed
is proportional to current
strength and time, and the
weight of substance
decomposed is proportional
to the equivalent weight
of the substance.

64
Since electrolysis broke up chemical
compounds, it was assumed that
electricity was concerned in some
way with affinity, an idea that
had preoccupied chemists.
Berzelius assumed that
every atom has different degrees of
excess positive or negative
charge. When compounds
are formed there is a
neutralization of
charges, but the
resulting
compound is
not For example,
necessarily sulphur,
neutral since the charges electropositive with
on the two reactant respect to oxygen,
atoms are unequal could combine with it to
and don’t form the binary compound
neutralize each sulphur trioxide, SO3, in
other exactly. which the
negative
charge
predominates,
leaving the
compound as a whole
electrically negative.
Similarly, potassium and
oxygen combined to give the
oxide K2O, which retains
positive charge. Therefore the
oxides of sulphur and potassium
could combine to form the salt
potassium sulphate.

+ve K -ve O +ve S -ve O

+ve K2O -ve SO3

6565 Potassium Sulphate

 This theory fit the facts of electrolysis well and gave
and explanation of the forces of affinity that held salts
together. However, it went against some experimental
facts, for example that the actual compounds SO3 and
K2O were not electrically charged. It also had some
other defects, like it made it impossible to accept
Avagadro’s theory in which two similarly charged
atoms of hydrogen, oxygen or nitrogen were united
with each other. This difficulty would become more
evident with later developments of organic chemistry
and was a chief factor in its downfall.

The theory was not generally applicable, but it did

well to explain the interaction of acids, bases and salts,
and is still essentially a part of our explanation of the
nature of ionic compounds.

At this time, chemistry for the first time was fully

recognized as a profession in its own right. Professors of
chemistry became more common in universities. Earlier,
chemists were often trained as pharmacists or physicians
before they undertook chemical investigations.

That’s our new chemistry Shocking! They never

professor, grandma... taught that sort of
thing at University in
my day!

66
The international character But I have
of science and free scienific
exchange of ideas helped immunity!
greatly in its growth. A
great example of this is the
fact that in 1813 Davy was
able to visit France and
travel through the
laboratories as a guest of
French chemists, though
England and France were in
the midst of the
Napoleonic wars.

Let us now look at the development of

organic chemistry.
Hello, we are the Organic family! And
we share great organic chemistry with the
Halogen family!

The products of a living organism, organic compounds, were

thought to be controlled by a special “vital force” exerted by
life itself that gave distinctive properties to organic
compounds. This view of Berzelius and most other scientists,
was challenged when in 1828 German chemist Friedrich
Wöhler (1800 – 1882) synthesised urea, a typical product
of the animal body, by evaporating an aqueous solution of
ammonium cyanate, an inorganic salt.
NH4 CNO [ammonium cyanate] > CO(NH2 )2 [urea]
67
 Most fascinating!
Urea without a
ler
Wöh kidney!

Wöhler’s discovery
refuted the vital force
theory. In a letter to
Berzelius, whom he had
been associated with,
Wöhler wrote,
“I must tell you that I
can prepare urea
us
without requiring the
eli
rz

kidney of an animal,
Be

either man or dog”.

This was a big step. As more compounds were

synthesised it became clear that organic
chemistry and biological processes are
governed by the same laws as those that
govern nonliving matter.

A great interest arose in synthesising organic

compounds from nonliving substances, like coal
tar and petroleum, and eventually, led to the
boom in German academic and industrial organic
chemistry in the second half of the 1800s.

68
 Justus Liebig (1803 – 1873)
contributed greatly to analytical organic
chemistry. He developed a method by Lie
car big w
which the numbers of each type of atoms He bon ent
in a molecule could be obtained. He do fina diox on a
w l i
burned a weighed sample of organic this n an ly tr de ch long
wa app d t cke ase a
substance and trapped the gases sol s fill arat rapp d it .
formed (chiefly carbon dioxide and po ution ed w us w ed it
t i h
water) with appropriate chemicals. From ash! of c th a ich in
aus
the increase of weight of the chemicals tic
he could see how much weight had been
added by the trapped products and
from this he could determine the amount
of carbon, hydrogen and oxygen in
the original substance.

nal
io t
nct s tha a
fu om as Radicals of the
o f a of at oped g world unite! We
p t p e l d in
e u v have nothing to lose
o nc gro t, de rstan the s but our bonds!
e c
p, a
u ni de . At oup
Th ou n
an in u istry e gr ls’.
r a s s
g ct
i d ea hem the ica at
a c , d h
re key nic ver ‘ra ed t some
ga we as er s
or , ho wn cov und . s
im e
k no d i s
m p o
ties ed a l
t re s
ist co per sifi ta
we hem give pro clas men c.
C als ir e da et
ic the wer ‘fun ols,
d of ds or oh
ra
o un ons , alc
o mp carb cids
C ro a
yd a ls’,
h
dic Those radicals are always
ra forming groups! Say they
want to change the world...
69
1837. J. B. A. Dumas (1800 – 1884) and
Justus Liebig said, “Radicals are the elements of
organic chemistry. In mineral chemistry the radicals
are simple while in organic chemistry the radicals are
compounds; that is all the difference. The laws of
combination and of reaction are otherwise the same.”

In the 1850s, the work of several chemists

culminated in the development of the idea of
molecular structure.

1852. Edward Frankland (1825 – 1899)

found that in case of nitrogen, phosphorus and
arsenic, an atom of these elements always
combined with three or five organic radicals.
Zinc, mercury and oxygen combined with two.

Frankland said, “ The combining power* of the

attracting element is always satisfied by the
same number of uniting atoms, no matter what
the character of the atoms is. It is like every
atom has a certain number of hooks by which it
attaches to other atoms or radicals.”
H
H

* The term combining

power was variously
expressed by other
scientists as
atomicity or affinity
C
units or valence.

H
H 70
The inner constitution of the
radicals was now considered.
Almost simultaneously,
Friedrich August Kekule
(1829 – 1896) in Germany
and Archibald Scott
Couper (1831 – 1892) in
as e
Paris approached this nd, ple
If fou o
problem independently and t
return per
developed the key idea in the ou
A.S.C
theory of organic chemistry -
that of structural formulas
formulas.

1858.
Carbon is ‘tetratomic’,
that is has four ‘affinity
units’ by which it can
unite with four
monatomic elements like
hydrogen and two
diatomic elements like
oxygen. Carbon can also
use one of its affinity
units to unite with
another carbon atom
and in this way chains of
carbon atoms could be
built up.

71

Kekule
 Kekule’s Modern
structures structures
○ propyl alcohol
○ ○ ○ ○ ○ ○ ○ ○ ○

○ ○ ○ acetone ○ ○ ○ ○ ○ ○ ○

Organic
compounds ○ ○ ○ benzene ○ ○ ○ ○ ○ ○ ○

can be
represented
by
diagrams. chlorobenzene
○ ○ ○ ○ ○ ○ ○ ○ ○ ○

dichlorobenzene
○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Kekule’s diagrams were not very convenient for visualization

of the actual structure. Couper developed the same theory
as Kekule, but expressed the links between the atoms by lines
thus giving the modern structural formulas.

The nature of most compounds could be understood,

but the structure of aromatic compounds like
benzene remained a mystery.

1865. Kekule was thinking hard about

this. The story goes that he dreamt of a
snake forming a circle by biting its own
tail. The image inspired him to picture a
carbon chain bending and uniting with
itself to form a ring. From this he
deduced the structure of benzene. His
remarkable ability of visualizing the
structure of carbon skeletons in organic compounds
was perhaps due to his early training in architecture.
72
 The structure of carbon compounds was

extended by Jacobus Henricus van’t Hoff

(1852 – 1911) and J. A. Le Bel(1847 – 1930)
who pictured the valence bonds of carbon, not
just in a 2-dimensional plane but directed
uniformly in 3-dimensional space. Thus the
carbon atom was at the centre of a tetrahedron
with the bonds directed along the corners of the
tetrahedron.

This could explain

stereoisomerism – two
compounds having the same atoms
and atomic connectivity but
different orientation of the atoms
in space – a phenomenon studied
by Louis Pasteur
(1822 – 1895) in 1848.
Pasteur noted that solid
sodium ammonium
tartrate existed as a
mixture of two types of
crystals, which he painstakingly
separated with tweezers. When plane-
polarized light passed through separate
solutions of these two types of crystals,
the plane of the light rotated in exactly
opposite directions. Past
eur
’s cry
stals

73
Several new elements were discovered in the 19th
century. This was facilitated by the introduction of
spectroscopic analysis.

Scientists had observed that sodium and potassium

salts produce characteristic colours in a flame.
Robert Bunsen (1811 – 1899) and Gustav Robert
Kirchhoff (1824 – 1887) in 1859 built a new instrument, a
spectroscope to study the light emitted by elements
when in a flame. The spectroscope mapped the
different frequencies of the emitted light.

This
i
Kirc s the spe
hhof ctro
the p f sc
ictu used. Th ope tha
re w t
as in e gas bu Bunsen
vent rner and
ed b
y Bu shown in
nsen
in 18
56.

Atomic emission spectra of a few elements.

Note that each element has different lines from the other.

74
 Each element emits
characteristic
frequencies of light
or lines in the
spectrum and these
are not affected by
the presence of other
elements.
Bunsen

Minute traces of an
element are
sufficient to give its
characteristic
spectrum or
fingerprint. If there
are lines in the
spectrum we have
not seen before,
they must belong to
a new element.
Kirchhoff

Spectroscopic analysis was an extremely sensitive

technique and led to the discovery of several
elements. The earliest of these were caesium
(caesius is sky blue in Latin) in 1860 and rubidium in
1861, which were named because of the beautiful
blue and red lines in their respective spectra.

75
As more elements became
known, certain trends were
recognised. Elements could
be organised into groups
based on the analogous
properties and reactions of
their members. The
halogens and the alkali
metals showed these
analogies clearly. At
the same time, the
atomic weights determined
by Berzelius gave a set of
numerical values in terms of which
some classification might be sought.

1869. Lothar Meyer (1830 – 1935) in

Germany and Dmitri Ivanovich Mendeleev
(1834 – 1907) in Russia simultaneously observed:

“If we arrange the

elements in the order
of increasing atomic
weight, a periodic
recurrence of
properties, physical
and chemical can be
noted.”
Meyer Mendeleev

76
They left vacant spaces where an element should fit
into a family group but where such an element was
not yet known.
“The table can predict the chemical
and physical properties of the
elements that should occupy the
vacant places in the table!”

First form of Mendeleev’s periodic table, 1869

The elements gallium, germanium and scandium were unknown

at the time and Mendeleev left spaces for them in his table and
even predicted their atomic masses and chemical properties.
Observed
○

Predicted
○
○

Eka-aluminium Gallium
○
○
○

Atomic weight: about 68 Atomic weight: 69.9

○
○
○

Metal of specific gravity 5.9; Metal of specific gravity 5.94;

○

melting point low; non-volatile; melting point 30oc; non-volatile at

○

moderate temperatures; not

○

unaffected by air; should

○

decompose steam at red heat; changed by air; no reaction with

○

should dissolve slowly in acids steam; dissolves slowly in acids

○
○

and alkalis. Oxide formula Ea2O3; and alkalis. Oxide formula Ga2O3;
○

should dissolve in acids to form dissolves in acids to form salts of

○

salts of the type EaX3; the the type GaX3; the hydroxide
○
○

hydroxide should dissolve in dissolves in acids and alkalis.

○

acids and alkalis.

○
○

77
 In 1874, gallium was discovered and Mendeleev’s
predictions were found to be accurate.

Other discoveries followed and their chemical behaviour

matched that predicted by him. These led to the
acceptance of the periodic table and it contributed greatly
in systematizing inorganic chemistry.

In parallel to inorganic and organic chemistry, physical

chemistry developed greatly in the nineteenth century.
The three major fields of progress were chemical
kinetics, thermodynamics and electrochemistry.

“Hi! I am the Chem-monster of

the 19 th century... My heads
represent the different branches
of chemistry in my time.”
Kinetic
s
istry
Electrochem
s
ic
a m
yn
od
rm
he
T

PH
YS
IC
A
L ORG
A NI
C
IC
GAN
OR
IN

78
1850. Ludwig Wilhelmy (1812 – 1864)
studied the hydrolysis of cane sugar in the presence
of acids. He used the change in optical rotation to
know the sugar concentration, and for the first time
came up with a mathematical expression for a
chemical process.

Wilhelmy showed that: If Z represented the

concentration of sugar, the sugar loss (dZ) in the
time interval dT is given by the expression

–dZ/dT=kZ
where k is a constant. This is the rate expression
for a monomolecular reaction.

Around the same time, A. W. Williamson

(1824 – 1904) had seen that when a
reaction produces substances at a
definite rate, and when these
substances in turn react at a definite rate
to regenerate the starting
materials, a time must
come when a balanced
equilibrium is
reached. This was
the concept of
dynamic
equilibrium.

79
1877. Van’t Hoff defined orders of reactions
(first order, second order etc.) by classifying them
according to the number of molecules taking part.

Svant
Svantee Arrhenius (1859 – 1927) found,
“Not every molecular
collision in a mixture
leads to reaction. Only
active molecules, that
is, the ones having a
minimum activation
energy, will react.”
Arr
hen
ius

On the basis of these ideas, kinetics, that is studies

concerning reaction rates, became a recognized branch of
chemistry. It contributed greatly to an understanding of the
actual course of chemical reactions.

Several examples of catalysis had been made

by this time but the explanation remained
mysterious. There was speculation that
a catalytic force changed the energy
states of the molecules.

80
1894. Wilhelm Ostwald (1853 – 1932) gave
the modern view of a catalyst and related this phenomenon
to the field of kinetics: A catalyst is a substance that increases
reaction rates without altering the energy of the reactants and
products, of a chemical process. A catalyst works by providing
a pathway for the reaction having a lower activation energy,
thus allowing a larger fraction of molecular collisions to lead
to reaction.
Let us consider a situation to understand the role of
a catalyst: Imagine you are in the middle of a desert
and want to write on a piece of paper.

You can only keep it on the sand

for support, but this would be
a slow, difficult process.

However, if you had a clipboard to support the

paper, the process will become much faster.
After you have written on one sheet, you can
use the clipboard again for another sheet.

So, the clipboard is like a catalyst - it speeds up your writing

without itself changing.

81
 ch
o t (1 7 9 6 – 1832), a Fren
Sadi Carn tu dy of the effic
iency
r, in h is s es
Enginee lo p e d steam engin
d e v e
of the newly th e foundations
of
0 s la id e
in the 182 IC S a n d introduced th
N A M
THERMODY
e ntropy.
concept of

1842. German physician Robert Mayer (1814 –

1887), was impressed by the darker red colour of venous
blood in the tropics, as compared to cold climates. The
darker colour meant that there was more oxygen in the blood
returning to the heart. From this Mayer inferred that, in hot
climates, the body burned less (because it required less
energy) to maintain body temperature. This was the first step
towards the law of conservation of energy
energy, which Rudolf
Clausius woud later arrive at.
Hmmm... I’ve
stirred this coffee
for a long time...
why isn’t it

1845. James Prescott getting hotter?

Joule (1818 – 1889) observed

that churning a liquid increased
its temperature and from this
showed the equivalence of heat
and mechanical energy.

82
Rudolf Clausius (1822 – 1888) in 1865
suggested the name ENTROPY for a new
thermodynamic state function and offered his
well known summary of the two laws:

1.The energy of the world is constant.

2.The
disoen n
rder tropy (w
of a h
syst ich i s t
em) h
tend e meas
s to ur
a ma e of
ximu
m.

83
 The THIRD LAW of thermodynamics would come much
later.
Around 1905, Walther Nernst(1864 – 1941) while
studying the behaviour of substances at very low temperatures,
proposed one of the early version of the Third Law:

Physical activities of substances

tend to vanish as the temperature
approaches absolute zero.

-273.150C 0oC 30oC

Thermochemical studies were made independently of these

developments in thermodynamics.

1840. Germain Henri Hess

(1802 – 1850) observed,

“In a reaction, the same amount

of overall heat is evolved no ROUTE 1
matter how many intermediate ROUTE 2+ROUTE 3
steps take place before a final
product is obtained.”

This law of constant summation of heat was actually a special

case of the law of conservation of energy announced by Mayer
two years later.

84
1878. Josiah Willard Gibbs (1839 –
1903) at Yale, United States developed the concept of
chemical potential that determines the direction of
a chemical process: Chemical potential is analogous to
electric potential. Just as electric current flows from a higher
electric potential to a lower electric potential, when a
reaction occurs, matter “flows” from a higher chemical
potential to a lower chemical potential.

A motorcycle is powered by the

combustion of fuel, a spontaneous
chemical process. The fuel in the
tank is at a higher chemical
potential than the combustion
products (primarily carbon
dioxide and water)
leaving the exhaust.

Gibbs also introduced the phase rule, which relates the

number of components (C) and the number of phases (P,
like solid, liquid, vapour) in a system to the number of
degrees of freedom (F, the number of variables such as
temperature and pressure that can be varied independently)
by the equation

F=C+2-P
85
 Austrian Ludwig Boltzmann (1844 –
1906) made pioneering contributions to the field of
statistical thermodynamics. This field relates
averages of molecular properties to thermodynamic
quantities and describes thermodynamics at a
molecular level.

I know how that works... to

see if rice is cooked, I take
a sample from the lower
part of the pot and one
from the upper part. If the
rice is cooked in both parts,
then I can be sure that all
of it is cooked.

Much of kinetic theory of

gases followed from
statistical thermodynamics.
Applying the methods of probability
to describe the motion of
gas molecules, Scottish physicist

James Clerk Maxwell (1831 –

1879) along with Boltzmann was able to show that the velocities
of the molecules of a gas follow what we now call a Maxwell-
Boltzmann distribution – a probability distribution whose mean
and spread increases with increase in
temperature.

86
1877. Boltzmann published the most famous
equation of statistical thermodynamics.

S=kB ln W
W,
S is entropy, kB is a constant and W is a quantitative measure
of the disorder of a system. This gives a relation between
the thermodynamic quantity entropy and the statistical
quantity W. Statistical thermodynamics was developed at a
time when the atomic nature of matter was not generally
accepted, so Boltzmann’s theory did not receive easy
acceptance initially.

Svante Arrhenius, during his doctoral

work at the University of Uppsala, Sweden in
the early 1880s identified the basis for the
conductivity properties of solutions: When
certain compounds – electrolytes (for
example salts) – are dissolved in water, a
portion of it dissociates into positive and
negative ions. Ions are responsible for carrying
electricity through the solution.

Impossible! Maybe he is right.

Oppositely charged After all his
ions cannot exist theory does
separately in explain
solution. No observation.
doctorate for
Svante.

The scientific
community later
recognised his work
and in 1903, Arrhenius
was awarded Nobel
prize for chemistry
“for his electrolytic
theory of
dissociation.”

87
As the 19th century was drawing to a close, chemistry had
developed greatly. However, the nature of forces that held
molecules together remained unanswered. The solution
came with a major revolution of scientific ideas - the
coming of the theory of ...

quantum mechanics
mechanics.
To follow what led to this theory, let us begin with some
experimental observations.

1874. William Crookes (1832 – 1919),

in his studies with a cathode
ray tube noticed the turning
of a small paddle wheel placed
in the path of the rays.

He found that the rays could exert force and consisted of

particles. From their deflection in a magnetic field, he
concluded that they carry a negative charge.

1897. Joseph John Thomson (1856 – 1940)

used a high vacuum to avoid interference by ionization of
residual gases and made accurate studies of deflection of
cathode rays in electric and magnetic fields. From this he
could make better determinations of the charge to mass ratio
and velocity of the particles.

“Cathode rays consist

of negatively charged
particles with a mass of
1/1845 that of the
hydrogen atom.”

88
 (Sigh) I think
we will just go
The name “electron” had with electron,
been coined earlier for since we have
used it all
the charge of the along anyway...
particles that carry
electricity in conductors.

G. F. FitzGerald
(1851 – 1901) proposed that
the name electron be

Fit
applied to these particles

zG
era
and this was universally

ld
accepted.

1895. William Konrad Roentgen (1845 – 1923) used

black paper to cover a vacuum tube in which cathode rays were
being generated. He noticed that crystals of barium
platinocyanide placed near it fluoresced.

Some type of radiation was present and this could pass through
solid matter, such as flesh, and cast
shadows of denser objects, such as
bones.

These X rays, as Roentgen called

them, have since found great
application in physics and
chemistry as a spectroscopic
tool and in medicine as a
diagnostic technique. It is
also used in security
systems e.g. to
scan baggage
at airports.

89
1896. Antoine Henri Becquerel
(1852 – 1908)

“X rays caused fluorescence.

Perhaps the opposite is true,
that is fluorescing bodies
produce X rays.
These uranium salts are known to
fluoresce when exposed to
sunlight. I wonder if they will
produce X rays after exposing
them to sunlight. Let me keep a
photographic plate wrapped in
black paper along with some
uranium salt, ready for the
experiment tomorrow.”

A series of cloudy winter days

in Paris hindered his plans.

After few days he developed the photographic plate anyway.

“This is unbelievable, the plate is

fogged! There must be some new
kind of rays that are causing the
plate to fog. These must be
emitted spontaneously by the salt
and can pass through non-
transparent objects.”

Further studies showed that uranium was the source of

the radiation.

90
Marie Skolodowska Curie (1867 – 1934), a
young Polish scientist and her husband, the French physicist,
Pierre Curie (1859 – 1906), began studying this
phenomenon and suggested the name radioactivity for it.
They obtained a large supply of waste uranium ore, pitchblende,
from the Austrian government and worked on isolating uranium
from it. They soon discovered that the radioactivity from the ore
exceeded that expected from uranium.

There must be a new element in the

ore which is responsible for this
large radioactivity. We have to
isolate it!

“Yes, there is room

in my table for a
new element.”

Marie Curie

91
Marie and Pierre toiled incessantly on purifying a ton
of ore to a few grams of radioactive substance. They
succeeded in showing that the ore contained two new
radioactive elements, polonium and radium. By a long
series of laborious fractional crystallizations, they
finally isolated a small quantity of pure radium salt.

This salt was truly

another one of nature’s
surprises! It glowed in the
dark and emitted heat. It
produced sores on the
skin, sterilized seeds,
healed surface cancer,
electrified the air around
it and its radiation
penetrated solids.

92
Marie Curie continued to study the properties of
the new elements and wrote her doctoral
dissertation on radioactivity in 1903. In the same
year, she and her husband along with Henri
Becquerel shared the Nobel prize for physics. Eight
years later, after Pierre’s death, Marie received
another Nobel Prize this time in chemistry.

In 1899, Ernest Rutherford found

that two types of radiation were emitted from
uranium. He called these α and β rays and these
were later identified as helium ions and electrons
respectively. In 1900 Paul Villard
discovered a third type, the γ rays, which he
recognised as similar to X rays. It was also realized
that uranium was changing into some other
substance.
Rutherford and Frederick
Soddy (1877 – 1956) gave a
theory of atomic disintegration
among radioactive substances
resulting in the formation of
new substances. This was verified
and established by 1909.

Disintegration series

Uranium-238 Radium-226 Polonium-214

α α α
Thorium-234 Radon-222 Lead-210
β α β
Protactinium-234 Polonium-218 Bismuth-210
β α β
Uranium-234 Lead-214 Polonium-210
α β α
Thorium-230 Bismuth-214 Lead-206
α β
93
The next question was on the structure of the atom, that is,
to know the arrangement of the electrons and positive ions
within the atom.

J. J. Thomson said, “The

atom consists of uniform
positive charge through
which electrons are
distributed, much like
plums in a pudding.”

Rutherford and his students set up an experiment

where they bombarded very thin gold sheet with α
particles (emanating from radium) and observed the
trajectory of the α particles.

Most of the α− particle bombardiers passed right

through, but some of these very high energy particles
were deflected at a sharp angle as if they had struck
something. Rutherford announced his theory to
explain this in
1911.
“The atom is composed of a
heavy but relatively small
nucleus where the positively
charged particles are lumped
together and outside it an
equal number of negatively
charged electrons are in
motion around it.”

94
 The charge of the nucleus is equal and opposite to
the number of electrons and was given the name
atomic number

While studyin
radioactivity g
it was found
that lead obta
ined from
the disintegra
tion
series of uran
ium has
atomic weigh
t 206
and that from
thorium, ato
mic
weight 208.

“Atomic number is more

fundamental for an element than
atomic weight. Elements with
same atomic number but
different atomic weights, we will
ur
call ISOTOPES from the Greek
o no for ‘the same place’ that they
nh
mp i dy occupy in the periodic table.”
h sta Sod
k
dis ric
we ede
S Fr e
of
Soddy received a Nobel Prize for Chemistry in 1921. By this
time, he was deeply disturbed by the structure of the
political economy within which science operated. This
made him turn to a study of economics. His ideas about the
relationship between money and society have been
important in unorthodox traditions in modern economics.

95
To get back to the structure of the atom...

Rutherford’s atom was like

a miniature solar system. A
problem with this picture
was that since accelerated
charged particles emitted
radiation, an electron
orbiting the nucleus would
lose energy and fall into the
nucleus and the atom
would not be stable.

Niels Bohr (1885 – 1962) of Copenhagen addressed

this concern by applying the idea of quantization that was
developed by Max Planck (1858 – 1948) to the atom.

1913.
“Hello, I am a Niels Bohr doll. I
am made of similar shells that
fit into each other.
Niels himself was very clever. He
suggested that electrons can
revolve around the nucleus with
quantized angular momentum
and therefore in only certain
orbits or shells. In such a shell,
the electron does not radiate.
Electrons can jump between
shells by absorbing or
emitting energy. The
outermost shell is
responsible for the
chemical properties
of the element.”

96
96
The Bohr model was successful in explaining some properties
of atoms, particularly their observed spectra.

1916. G. N. Lewis (1875 – 1946)

and Walther Kossel (1888 – 1956) also
used the Bohr model to explain chemical
affinity or bonding:

“Inorganic ions were formed

by gain or loss of electrons in
the outer shell to complete a
STABLE OCTET with an
electric charge. These ions
were held together by
electrostatic forces forming
○
POLAR compounds with an ○ ○
IONIC BOND. Organic ○ ○
compounds, NON-POLAR in
character are held together
by sharing a pair of electrons
in a COVALENT bond.”

97
97
1925. Wolfgang Pauli (1900 – 1958) announced
his exclusion principle according to which each energy state
or orbit could hold only two electrons. Thus electrons
cannot just drop down to the lowest energy state. The
periodic table could be correlated to the arrangement of
electrons in the states.

Electrons occupy states, in a

manner similar to the way
passengers occupy seats in an
empty bus. The window seats
generally fill up first, starting
from the front of the bus. Once
the window seats are filled in the
bus, pairing begins, again from
the front. Similarly, electrons
prefer to be alone in a state and
begin pairing when energy states
are much higher in energy.

1924. Louis de Broglie (1892 – 1987)

proposed that material particles exhibit wavelike properties
under certain conditions, just as radiation was known to
exhibit particle like properties.

98
1925. Erwin Schrödinger
(1887 – 9161) and Werner Atoms and
molecules are
Heisenberg (1901 – 1976) described by a W ave
independently formulated a F unction which can
general quantum be calculated
theory, which would explain mathematically and
the behaviour of electrons, atoms which completely
and bonding of atoms in molecules. specifies the
system.

Old Au
strian 1
000 Schillin
g note
with Sc
hrö dinger’s
picture

HEISENBERG’S FORMULATION was based on matrix algebra, but

was shown to be Born
Max equivalent to the wave mechanics formulation.

1926.
“The physical interpretation of
the wave function of a particle is
that, its square at a particular
point is the probability density of
finding the particle there.”

99
99
We looked at the formulation of quantum
mechanics in the previous pages.

quantum mechanics.
theory, which is the ultimate basis of our
is the

understanding of chemistry today. It explains the

structure of the periodic table, molecular
structure, bonding, reactivity, spectroscopy and so
on. It thus unifies the different branches of
chemistry.

Quantum mechanics is
based on a set of
postulates or axioms, like
for example classical
mechanics is based on
Newton’s laws. The
axioms of quantum
mechanics are
however less
intuitive than
classical
mechanics and
we will not go
into them here.
The test of the
theory is that
it can explain
and predict
observation.

100
1930s. Quantum mechanics was applied to chemical systems
to understand the structure and properties of molecules. This is
Quantum cchemi
Quantum hemistry
hemistry
stry. One of the early champions of
quantum chemistry was Linus Pauling (1901 - 1994) who
developed a model to understand bonding called the valence-bond
approach. His book, with the almost magical sounding title The Nature
of the Chemical Bond, became one of the most influential works of the
time. An alternative approach to bonding was pioneered by
Friedrich Hund (1896 - 1997) and Robert Mulliken (1896 —
1986) called the molecular-orbital approach. These two approaches are
complementary, each providing its own insights into chemical bonding.

Douglas Hartree (1897 - 1958) and Vladimir Fock (1898 - 1974)

in the 1930s proposed a technique for the approximate calculation of
the wave function of the molecule.

1950s Clemens Roothan developed a method

where computers could be used to calculate the wave
function and molecular properties. This is the subject
area of Computational chemistry.

The methods have improved over the years and

computers have become faster. Today, before carrying
out a reaction in a laboratory (involving expensive
chemicals and equipment) a chemist sitting at her
computer can often get a reasonably accurate idea of
the outcome of the reaction using computational
chemistry. Of course, there are limitations of accuracy,
particularly as the chemical system becomes large and
so empirical studies continue to be important.

101
101
It is not possible to view atoms or molecules directly or using
any optical microscope. To look at structure and properties of
substances at a molecular level, the interaction of light or
electromagnetic radiation with atoms and molecules is
commonly used and forms the branch of study called
spectroscopy
spectroscopy..

Ever since the first spectroscopic analysis in 1859 of sodium

and potassium in a flame, several spectroscopic methods have
been developed which use different parts of the
electromagnetic spectrum (i.e. light of different frequencies)
to look at various processes.

For example...

Microwave absorption
spectroscopy is used to
investigate the rotation
of molecules and yields
moments of inertia and
bond lengths.

RAMAN SPECTROSCOPY,
which is based on a
phenomenon studied by
Chandrasekhara Venkata
Raman (1888 – 1970) can be
used to study the vibration
and rotation of molecules.
From the vibrational
behaviour of a molecule,
information concerning
the stiffness or rigidity
of its chemical bonds
can be obtained.

102
Nuclear magnetic resonance (NMR)
spectroscopy gives information about the
environment of an atom in a molecule and
also the arrangement
of its neighbouring
atoms. Just look at that...
isn’t it beautiful?

Spectroscopy plays
a role not only to
unravel the basic
chemistry at the
molecular level,
but it provides
an invaluable
tool to scientists
synthesizing new
compounds or designing new materials, by allowing
them to look at their products.

Spectroscopy is also used by analytical chemists in

pharmaceutical, petroleum and consumer
product industries, for quality evaluation.

Moreover, spectroscopic
techniques are frequently
applied in medicine. For
example, magnetic Resonance
Imaging (MRI) works on the
principle of NMR and is used
to scan for tumours in the
brain. It is also used by
scientists trying to understand
the functioning of the brain.

103
We have seen the close relation between the
development of chemistry and physics in the
beginning of the 20th century. The trend of
chemistry crossing borders and having more to do
with other disciplines, notably biology and material
science besides physics, has continued through the
twentieth century.

“Remember me? I am the Chem-monster you

met in the 1800s. It’s been more than a century
now - I’ve grown many more heads and become
a lot more complicated. That’s because
chemistry today is related to many other fields
and all these fields too, are inter-related.”

The diversity and growth of chemical research in

recent years has been simply enormous and in the
next few pages we will sample just a few of these
areas.
104
The 20th century has added several new chemical
elements to the periodic table, particularly those heavier than
uranium. Uranium has the highest atomic number (92) of the
naturally occurring chemical elements on earth. The effort to
synthesize artificial elements beyond uranium (transuranic
elements) began after Ir ène and Frédér
Irène édéricic Joliot-Cur
Joliot-Cur ie
t-Curie
discovered artificial radioactivity in 1934. They bombarded
light elements with alpha particles and produced radioactive
isotopes of known elements that are not found naturally. This
idea of bombarding with particles was used to create artificial
transuranic elements. The first such element was neptunium
(element 93), made in 1939.

Soon after in 1941 Glenn Seaborg (1912-1999) and his

Seaborg
associates made plutonium (element 94) and went on to
discover nine more transuranic elements. His last, element
106, was created in 1997 and named Seaborgium after him.
As of year 2006, element 118, with the temporary name
Ununoctinium, is the latest element to be created.

How many I don’t know how many will

elements are actually be made, though
there going to there is always room in my
be eventually? table for more!

105
The understanding of the Chemistry of Life
increased rapidly in the twentieth century.

Linus Pauling who we have met as a pioneer of quantum

chemistry, was a very versatile person. He worked on the
molecular structure of amino acids, which are the building
blocks of proteins, and in the late 1940’s determined the
fundamental structural pattern of many proteins, the so
called á-helix. In 1954 he was awarded the Nobel Prize in
chemistry.
Pauling was also a peace activist. In 1958, he presented to
the United Nations, a petition signed by 11,000 scientists
from many countries, protesting further nuclear testing.
His efforts were vindicated when a treaty was signed by the
then three nuclear weapon owning nations — the US, UK
and the USSR. Pauling was awarded a second Nobel Prize
for peace in 1962.

the
b ling g for
em in
g ass on ask they
l i n it i c h
Pau pet whi
e len for a sting,
a H sts te s.
d Av cienti apons ation
a n f s e N
us so rw ed
Lin ature nuclea Unit
e
sign nd to to th
n e t e d
a sen
pre
106
 The information about a living system is
passed to its future generation through a
polymer called deoxyribonucleic acid
(DNA). Together with other similar
nucleic acids called the ribonucleic acids
(RNA), DNA is also responsible for the
synthesis of the various proteins
needed by the cell to carry out its
life functions. From the chemical
composition of DNA and its X-ray
crystallography photos, its structure was
elucidated by JAMES WATSON (born
1928), FRANCIS CRICK (1916 – 2004),
MAURICE WILKINS (1916 – 2004) and
ROSALIND FRANKLIN (1920 – 1958) in
1953.

Today, the science of DNA, proteins and

other biomolecules has directed the

Sketch by Francis Crick, attention of a large body of chemists

showing his first mainly because of its potential medical
impression of the DNA
molecule. c.1953 implications.

107
Chemists have synthesised various naturally occurring
molecules in the lab. One of the most complex natural
compounds synthesised to date is vitamin B12. Robert
Burns WWooodwar
odward d (1917 — 1979) in collaboration with
Albert Eschenmoser (1925 —) and a team of
almost one hundred students and postdoctoral
workers worked for many years on the synthesis of
this molecule. The synthesis included almost a
hundred steps. It was completed in 1971 and is a
landmark in the history of organic chemistry.

In 1985, Robert Curl (1933 —), Harold Kroto (1939

—) and RiRicchar
hardd Sm alley (1943 —) made a sensational
Smalley
discovery of a new form of carbon. This stable
molecule of carbon had sixty carbon atoms arranged
in a closed shell like a soccer ball. Because of its
similarity in shape also to the “geodesic dome”
invented by architect Buckminster Fuller, they named
this new carbon molecule buckminsterfullerene.
Fullerene molecules have a beautiful structure and a
great amount of research has taken place since their
discovery to understand them better.

structure of buckminsterfullerene

108
A striking development in instrumentation was
made in 1981 when Gerd Binnig (1947 —) and
Heinrich Rohrer (1933 —) invented the
scanning tunneling microscope
(STM) based on the quantum mechanical effect of
tunneling. The instrument scans an electrical probe,
a sharp stylus, over a surface and detects a weak
electric current flowing between the tip and the
surface. The stylus is so sharp that its tip consists of
only one atom!
Based on the current it is possible to map the surface
of substances with amazing accuracy – to a point
where individual atoms can be recognized.

During a reaction, chemical This is like using the

events at the molecular level world’s fastest
occur rapidly and a technique camera to film the
molecules during the
to observe these was developed reaction and to get a
at the end of the 1980s, sharp picture
of the
pioneered by Ahmed Zewail transition
(1946 —). Short intense flashes state.
of light that are a femtosecond
(10-15 second) in duration are
followed by spectroscopic
analysis. This is the timescale
on which chemical bonds are
formed or broken and using
this technique and relevant
theoretical methods, we are
able to understand reactions in
unprecedented level of detail.

109
A commercial revolution has come
about because of the industrial
application of chemistry. Today plastics,
rubbers, alloys with specific properties,
catalysts to speed up industrial
processes and materials for electronic
technology are being used and invented
like never before.

Let us consider the timeline of a class

of industrial products – synthetic
polymers or plastics. The first
completely synthetic plastic was Bakelite
invented in 1907 by Leo H. Baekeland
(1863 – 1944). It was a rigid, lightweight
material and used to make everything
from hairbrushes to handles of frying
pans. Wallace Hume Carothers (1896 –
1937) developed a new polyamide fibre
which was marketed as ‘Nylon’ in 1938.
In the early 1950s a new process for
synthesizing polymers was discovered
that made a lot of common plastics
possible, including high-density
polyethylene and polypropylene. Karl
Ziegler (1898 – 1973) and Giulio Natta
(1903 – 1979) were just two of several
scientists who independently developed
the process. Most polymers are
insulators but in the late 1970s it was
discovered that polymers can also
conduct electricity. Conductive
polymers are promising because they are
much lighter than metals and potentially
cheaper. They may play a very important
role as conductors in the future.
110
110
Chemistry has made our material lives more
comfortable than ever before, but the massive
scale of industries and chemicals has also had
an impact on the environment.

An example is the case of chloroflurocarbons

(CFCs) developed as a replacement for
ammonia in refrigerators and also used as a
propellant in spray cans. These CFCs are
inert and able to reach the upper atmosphere
without reacting, where they are decomposed
by ultraviolet light from the sun, releasing
chlorine atoms. Chlorine then combines with
ozone, thus depleting the protective ozone
layer of the earth. CFCs are being phased
out since the 1990s, but this experience
demonstrated the unforeseen consequences
of the widespread use of a seemingly benign
substance.

The challenge of protecting our environment

while providing our needs presents
opportunities to chemistry and science as a
whole. We have seen chemistry bridging
boundaries with other disciplines. We can
hope that the resulting understanding of
issues from a broader perspective, will help
us overcome these challenges. It may form an
interesting future chapter in the story of
chemistry. We will have to wait and see.

111
111
 PERIODIC TABLE OF THE ELEMENTS
Dmitri Mendeleev (1834-1907)
The Russian Chemist, Dmitri Mendeleev, was the first to observe that if elements
H were listed in order of atomic mass, they showed regular (periodical) repeating
Hydrogen properties. He formulated his discovery in a periodic table of elements, now regarded
1 as the backbone of modern chemistry.
The crowning achievement of Mendeleev’s periodic table lay in his prophecy of
then, undiscovered elements. In 1869, the year he published his periodic
classification, the element gallium, germanium and scandium were unknown.

Mendeleev left spaces for them in his table and even predicted their
Li Be atomic masses and other chemical properties. Six years later, gallium
Lithium Beryllium was discovered and his predictions were found to be accurate. Other
3 4 discoveries followed and their chemical behaviour matched that
predicted by Mendeleev.
The remarkable man, the youngest in a family of 17 children, has left
the scientific community with a classification system so powerful that
it became the cornerstone in chemistry teaching and the predication
Na Mg of new elements ever since.
Sodium Magnesium In 1955, element 101 was named after him: Md - Mendelevium.
11 12 In this remarkable chart, originally prepared by the South African
Agency for Science & Technology Advancement (SASTA) the elements
are shown with an item of daily use. The symbols, names and atomic
numbers of the elements are given.
Redrawn by - Dr. Vidula Mhaiskar
K Ca Sc Ti V Cr Mn Fe Co
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt
19 20 21 22 23 24 25 26 27

Rb Sr Y Zr Nb Mo Tc Ru Rh
Rubidium Strontium Yitrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium
37 38 39 40 41 42 43 44 45

Cs Ba Hf
Lanthanide Hafnium
Ta W Re Os Ir
Caesium Barium Tantalum Tungsten Rhenium Osmium Iridium
55 56 series 72 73 74 75 76 77

Fr Ra Actinide Rf Db Sg Bh Hs Mt
Francium Radium series Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium
87 88 104 105 106 107 108 109

112
 He
Helium
2

B C N O F Ne
Boron Carbon Nitrogen Oxygen Fluorine Neon
5 6 7 8 9 10

Al Si P S Cl Ar
Aluminium Silicon Phosphorus Sulphur Chlorine Argon
13 14 15 16 17 18

Ni Cu Zn Ga Ge As Se Br Kr
Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
28 29 30 31 32 33 34 35 36

Pd Ag Cd In Sn Sb Te I Xe
Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
46 47 48 49 50 51 52 53 54

Pt Au Hg Tl Pb Bi Po At Rn
Platinum Gold Mercury Thalium Lead Bismuth Polonium Astantine Radon
78 79 80 81 82 83 84 85 86

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
57 58 59 60 61 62 71 63 64 65 66 67 68 69 70
Lanthanide Series

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinide Series

113
114